Co-precipitated carrageenan/xanthan gum compositions and processes for their preparation

ABSTRACT

Co-precipitated carrageenan/xanthan gum compositions and a process for preparation are provided. The compositions are simple to prepare and provide functional performance in a broad range of food, specialty and industrial applications.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is directed to co-processed carrageenan/xanthancompositions, methods of manufacture, and formulations containing suchco-processed products.

2. Description of the Related Art

Various hydrocolloids and combinations thereof are known for use in thefood industry. Carrageenan-based systems conventionally prepared byadmixing crude or purified carrageenan gelling agent with one or moreother hydrocolloids or gums are used to provide compositions or gelswidely used as thickeners or gelling agents for prepared foods.

Known mixed gel systems intended for use in food or dentifriceapplications are commercially dependent on convenient and economicalextraction, purification and clarification techniques for obtaining thecomponents substantially free of undesirable impurities and which, uponinteraction with a gelling agent, produce clear, stable gels.

U.S. Pat. No. 4,569,838 (de Vries) discloses a dentifrice havingdesirable rheological properties suitable for facile extrusion from aflexible dentifrice tube. The dentifrice includes a siliceous polishingmaterial, an anti-nucleating agent and a gelling agent mixture ofiota-carrageenan and xanthan which is prepared by physical mixing ofiota-carrageenan and xanthan.

In the curing of meats, the dressed meat is usually injected with abrine solution, typically by multi-needle injection or by stitch orartery pumping. The injection may be followed by resting, tumblingand/or massaging and finally cooking. Alternatively, the meat may betumbled or massaged in the brine solution. Some standard picklingprocedures are disclosed in U.S. Pat. Nos. 3,565,539; 3,683,789 and3,922,357.

There is a tendency for the injected brine to leak out of distributed,uncooked food products in either fresh, chilled or frozen condition,during distribution or sale or at the final customer. Thus, there is aneed to reduce leakage or liquid seepage from meat products into whichbrine solution has been incorporated. This tendency may be measured as“drip loss” and may be measured for products which have been speciallypackaged, e.g. under vacuum or reduced pressure, or for products whichhave been packaged without vacuum or reduced pressure.

In addition, food products into which brine solutions are incorporatedmay also suffer from the problem of excess weight loss during cooking.Thus, the incorporated solution may leak out during cooking, creating ahigher than acceptable weight loss in the product.

One prior art technique for addressing this problem is to add sodiumchloride and/or sodium tripolyphosphates to meat products in order toincrease the water-binding capacity of the meats. However, thistechnique may be undesirable in certain applications due toconsiderations such as the sodium and phosphate contents of theresultant meat products which may adversely impact their consumerappeal.

In the prior art, it is known to mix brine and gelling polysaccharidessuch as carrageenan or gellan to provide a solution for injection intofood products. U.S. Pat. No. 6,685,978 (Hauksson) discloses a processfor forming a food treating composition by mixing water, a gellablepolysaccharide and a gelling cation. The gellable polysaccharide maycomprises at least one of carrageenans and carrageenans in combinationwith at least one of locust bean gum, cassia gum, or konjac gum, xanthangum and xanthan gum in combination with seed gums, meal or flour ofseaweeds containing gelling polysaccharides, either treated oruntreated. Preferably, the polysaccharide comprises one or more of iotacarrageenan, kappa carrageenan, xanthan gum and low ester pectins.

Gelcarin® ME 4951 stabilizer from FMC BioPolymer comprises a mixture ofcarrageenan and xanthan. This stabilizer is recommended for use in themeat processing industry for injection and tumbling when making cookedham. Brines made with this stabilizer are said to show little or nosedimentation upon standing without stirring and to result in adecreased cooking loss.

Viscarin® SD 2069 stabilizer from FMC BioPolymer comprises a mixture ofxanthan and carrageenan with sugars for standardization. This stabilizeris recommended for use to thicken and stabilize spoonable saladdressings, mayonnaise, sauces and gravies.

Gelcarin® DX 7150 stabilizer from FMC BioPolymer comprises a mixture ofcarrageenan, calcium lactate, xanthan gum and sugars forstandardization. This stabilizer is recommended for use in dry mix cakeglazes.

Danagel® AF 9050 stabilizer from FMC BioPolymer comprises a mixture ofcarrageenan, xanthan and calcium lactate. This stabilizer is recommendedfor use in specialty fragrance gels with high clarity.

Gelling compositions for food products may be prepared in a number ofways. U.S. Pat. No. 5,498,436 (Modliszewski et al.), for example,discloses a composition comprising: (A) a co-precipitate consistingessentially of: (a) a galactomannan, with (b) a glucomannan, and (B)optionally a gelling agent admixed with the formed co-precipitate.Gelling agents, such as carrageenan may be mixed with the co-precipatedproduct after co-precipitation. Co-precipitation of components (a) and(b) was found to increase the cold solubility of the composition ascompared to a physical mixture of the same components.

U.S. Patent application publication no. US 2002/0019447 A1 disclosesmethods for the clarification of hydrocolloids such as carrageenans andxanthan. In addition, this publication discloses the co-precipitation ofa series of hydrocolloid pairs in the examples. A similar disclosure isfound in U.S. Patent application publication no. US 2005/0070704 A1.

U.S. Pat. No. 4,952,686 (Renn et al.) discloses soluble cassia alloy gumcompositions and processes for making them. One such composition is aco-precipitated combination of cassia gum extract and carrageenanco-precipitated using isopropyl alcohol. The co-precipitated materialmay be used for absorbing aqueous media.

Despite the foregoing, there remains a need for improved hydrocolloidcompositions for use in food and dentifrice products to provide areduction in leakage or drip loss for injected or tumbled foods, or toimprove the rheological properties of a dentifrice.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows Brabender hydration profiles for aqueous solutions of 2% byweight of 75:25 weight ratio of co-precipitated iota carrageenan/xanthan(Example 1-3) and 2% by weight of a dry blend mixture of 75% iotacarrageenan and 25% xanthan (comparative example), respectively.

FIG. 2 shows Brabender hydration profiles for toothpaste elixirs with1.6% by weight of a 75:25 weight ratio of co-precipitated iotacarrageenan/xanthan (Example 1-3) and 1.6% by weight of a dry blendmixture of 75% iota carrageenan and 25% xanthan (comparative example),respectively

FIG. 3 shows drip loss as a function of time for uncooked pork loinsafter injection (target 125% of original weight) with brines containing2.5% iota carrageenan (non-inventive control example), 2.5% of dry blend(75% iota carrageenan and 25% xanthan) (comparative example) or 2.5% ofco-precipitated 75:25 iota carrageenan/xanthan (Example 1-3),respectively.

FIG. 4 shows the overall cooked process yield of pork loins cooked to aninternal temperature of 165° F. (74° C.) that had been injected (target125% of original weight) with brines containing 2.5% iota carrageenan(non-inventive control example), 2.5% of dry blend (75% iota carrageenanand 25% xanthan) (comparative example) or 2.5% of co-precipitated 75:25iota carrageenan/xanthan (Example 1-3), respectively.

FIG. 5 shows drip loss as a function of time for uncooked whole chickensafter injection (target 120% of original weight) with brines containing2.5% iota carrageenan (non-inventive control example), 2.5% dry blend(75% iota carrageenan and 25% xanthan) (comparative example) or 2.5% ofco-precipitated 75:25 iota carrageenan/xanthan (Example 1-3),respectively.

FIG. 6 shows drip loss (%) versus post-injection refrigerated time forbrine injected fresh processed meats with a target injection level(extension level) of 125% of the weight of the meat immediately prior toinjection using a co-precipitate (Brine B of Example 7) in accordancewith the present invention, as well as comparative examples with astandard carrageenan-containing brine solution and a phosphate brinewhich did not contain carrageenan. This figure shows that the productsof the invention can be customized for meat products that requiredifferent storage periods, thereby providing economic advantages, e.g.by reducing use levels for meats requiring shorter storage periods.

FIG. 7 shows hold times as a function of usage and extension levels forBrine B of Example 7 injected into fresh processed meats. Again, thisshows the ability of the products of the invention to be customized byvarying use levels for meats requiring storage periods of differentlengths.

FIG. 8 shows cooking yields for brine injected fresh processed meatswith a target injection level (extension level) of 125% of the weight ofthe meat immediately prior to injection using a co-precipitate (Brine Bof Example 7) in accordance with the present invention with and withoutphosphates, as well as comparative examples with a standardcarrageenan-containing brine solution and a phosphate brine which didnot contain carrageenan.

FIG. 9 shows comparative yields after different hold times for brineinjected fresh processed meats with a target injection level (extensionlevel) of 125% of the weight of the meat immediately prior to injectionusing a co-precipitate (Brine B of Example 7) in accordance with thepresent invention, as well as comparative examples with a standardcarrageenan-containing brine solution and a phosphate brine which didnot contain carrageenan.

FIG. 10 shows the ability to replace phosphates in brine solutions witha brine solution containing a co-precipitate according to the presentinvention (Brine B of Example 7) and containing sodium citrate in termsof comparative yields (percent loss of weight) over time.

SUMMARY OF THE INVENTION

In a first aspect, the present invention relates to a co-precipitatedhydrocolloid composition including at least one carrageenan and at leastone xanthan (hereinafter also referred to as “the co-precipitate”).Typically, said carrageenan and xanthan are present in an amount of60:40 to 95:5, respectively, based on weight percentage. The presentinvention also relates to compositions containing the co-precipitate.

In a further aspect, the present invention relates to toothpastecompositions including the co-precipitate of the present invention. Thetoothpaste may include at least one of water, a humectant, a surfactantand an abrasive.

In another aspect, the present invention relates to a dry compositionincluding the co-precipitate of the present invention and at least oneadditional hydrocolloid.

In a further aspect, the present invention relates to a process forpreparing a co-processed hydrocolloid including the steps of mixinghydrated hydrocolloids including at least one carrageenan and at leastone xanthan, and co-precipitating the mixed hydrocolloids to recover aco-precipitated hydrocolloid from the aqueous medium.

In another aspect, the present invention relates to a process fortreating an uncooked food product comprising at least one of meat,seafood and poultry, comprising the step of adding to the uncooked foodproduct an aqueous composition comprising the co-precipitate.

In another aspect, the present invention relates to a food product madeby adding to an uncooked food product comprising at least one of meat,seafood and poultry, an aqueous composition comprising theco-precipitate.

These and other aspects of the present invention will be apparent fromthe detailed description of embodiments of the invention and theexamples which follow.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The co-precipitated hydrocolloids described herein contain two or morechemically different hydrocolloids, one of which is a carrageenan andanother of which is a xanthan gum. These hydrocolloids are preferablyprepared in a manner which produces a substantially homogeneous product,as distinguished from a two component physical mixture (“dry blend”) ofa carrageenan and a xanthan gum. A substantially homogeneousco-precipitated carrageenan/xanthan product may have some minorvariations in the relative concentrations of the two co-precipitatedcomponents at particular locations in the product and the product cannotbe mechanically separated into individual components.

Carrageenan (also called carrageenan gum) is a commercially significantgalactan polysaccharide found in red seaweed. All carrageenans containrepeating galactose units joined by alternating α1→3 and β1→4 glycosidiclinkages and are sulfated to widely varying degrees. The types ofcarrageenan may be distinguished, in part, by their degree and positionof sulfation, as well as the seaweed from which they are obtained. Thevarious types of carrageenan include kappa, kappa-2, iota, lambda, muand nu. Because carrageenans vary in their composition and structure,they are known to vary in properties and uses. Carrageenans also vary inmolecular weight, cation content and cation type.

Carrageenan is a hydrocolloid which may consist of one of more of thepotassium, sodium, magnesium, calcium, zinc and ammonium sulfate estersof galactose and 3,6-anhydrogalactose copolymers. These hexoses arealternately linked α-1,3 and β-1,4 in the polymer. The relativeproportions of cations existing in carrageenan may be changed duringprocessing.

Since carrageenans are known to have varying properties, the type ofcarrageenan used for a particular product may be selected based on thedesired end use and the properties of the carrageenan suitable ordesirable for that end use. For example, different carrageenans gel withdifferent salts allowing some customization of the materials insituations where gelation is desirable.

Xanthan (also called xanthan gum) is a microbial exopolysaccharideproduced by the naturally occurring bacterium Xanthomonas campestris. Itis a widely used biopolymer in the food and pharmaceutical industries.It is also used in many other fields such as petroleum production,pipeline cleaning, enhanced oil recovery, textile printing and dyeing,ceramic glazes, slurry explosives and in cosmetics and oral care.Xanthan is typically used for the purposes of thickening, suspending,stabilizing and gelling.

Xanthan consists of a pentasaccharide repeating subunit. It consists oftwo D-glucopyranosyl units, two D-mannopyranosyl units and aD-glucopyranosyluronic acid unit as determined by methylation analysisand uronic acid degradation. The molecule has a (1,4) linked(β-D-glucopyranosyl backbone as found in cellulose, with atri-saccharide side-chain attached to the 0-3 position on alternateglucosyl units. The side chain is constructed such that theD-glucuronosyl unit is flanked by the two mannosyl units. Approximatelyhalf of the terminal D-mannosyl units have a pyruvic acid moiety acrossthe O-4 and O-6 positions. The other D-mannosyl unit is substituted atthe O-6 position with an acetal group. Xanthan is available readily asthe sodium or potassium salt, or as mixtures of sodium, potassium orcalcium salts, and at varying levels of pyruvate. Xanthan has beenestimated to have a molecular weight between 2 million to 50 millionDaltons. This wide range of values is believed to be due to polymerchain association.

Co-processing is done by a method of co-precipitation of a carrageenanand a xanthan. The co-processing method typically includes the steps of:(A) mixing a carrageenan, or seaweed containing carrageenan, with anaqueous medium (optionally accompanied by heat and/or agitation, and/oralkali) to form a carrageenan sol containing hydrated carrageenan; (B)mixing xanthan in a similar manner with the same aqueous medium as thecarrageenan in (A), or in a separate aqueous medium, to form a xanthansol containing hydrated xanthan; and, if the carrageenan sol and xanthansol were prepared separately, co-mixing the carrageenan sol and xanthansol to form a co-mixture of hydrated carrageenan and hydrated xanthan;(C) optionally clarifying the carrageenan sol, the xanthan sol, or theco-mixture of hydrated carrageenan and hydrated xanthan to removeinsoluble solids; (D) optionally concentrating the solids of theco-mixture of hydrated carrageenan and hydrated xanthan by any effectivemeans, such as evaporation or ultrafiltration; (E) co-precipitating theco-mixture of hydrated carrageenan and hydrated xanthan to form aco-precipitate, preferably by the addition of an organic solvent that ismiscible with the aqueous medium, or other effective precipitationmeans; (F) separating the co-precipitate from the aqueous medium; (G)drying the co-precipitate, and (H) optionally grinding the driedco-precipitate to a finer powder.

The total solids concentration during co-processing, and the temperatureof processing, may vary according to tradeoffs known in the art. Highersolids concentrations and lower processing temperatures are advantageousin increasing process efficiency, but the same conditions raise theviscosity of the solution and make processing more difficult. Theoptimal balance depends on the details of the processing equipment used.In general, a maximum total concentration of the carrageenan and xanthanin the processing medium, on initial mixing to form the co-mixture, ofno more than about 10.0 wt %. A concentration of 1.0 to 3.0% isrecommended for optimum processing, and a maximum total gumconcentration range of from about 1.5 to 2.5 wt % is often preferable.Where a clarified co-precipitate is desired, it is of particularimportance to adjust the total solids content of the processing mediumto facilitate filtration of the co-mixed sols; a total solids content of0.5 to 3.0%, more preferably, from about 1.0 wt % to about 2.0 wt % isdesirable for ease of processing when clarification is desired.Processing is dependent on the viscosity of the co-mixture and thegelling temperature of the co-mixture. Some embodiments allow for highersolids concentrations of up to 10% during processing, by loweringmolecular weight or reducing the level of cations that may contribute togelation.

The co-precipitation of the carrageenan and xanthan is critical to thisinvention, however, the co-precipitation step may be carried out by anyeffective means which provides a substantially homogenous precipitateand does not result in significant isolation and separation of one ofthe carrageenan and xanthan components. Examples of suitableco-precipitation means include co-precipitation by use of organicsolvents, drum drying, spray drying, air drying, fluid bed drying andfreezing followed by pressing or drying. Co-precipitation drying methodsare preferred. Co-precipitation with a water-miscible solvent andpossible pH adjustment is even more preferred. Co-precipitation withalcohols, and especially with isopropyl alcohol, is the most preferredco-precipitation method.

The amount of alcohol solution sufficient for co-precipitation will varywith the co-precipitation conditions, but addition of two or more partsof isopropyl alcohol (at about 65-85% isopropyl alcohol) to one part ofthe co-mixture solution is an effective precipitant. Lower ratios ofalcohol solution to co-mixture may be effective, depending on details ofthe process conditions, such as gum concentration and temperature. Loweraddition ratios, such as 1.5 parts of alcohol solution to 1 part ofco-mixture, or 1 part of alcohol solution to 1 part of co-mixture arepreferred when effective for co-precipitation. The carrageenan cancomprise from 1 wt % to 99 wt % of the co-precipitate (based on gumsolids), but usually comprises about 50 wt % to 90 wt %, preferably 60wt % to 80 wt % of the co-precipitate, and in some more preferredembodiments the carrageenan comprises 70 wt % to 80 wt % of theco-precipitate, based on the total dry weight of the polysaccharidescontained in the co-precipitate.

In one embodiment, the present invention relates to co-precipitatecompositions consisting essentially of the co-precipitatedcarrageenan/xanthan. In another embodiment, the present inventionrelates to compositions consisting of the co-precipitatedcarrageenan/xanthan. Preferred compositions of these embodiments havecarrageenan/xanthan weight ratios of 60:40 to 95:5. More preferredcompositions have carrageenan/xanthan weight ratios of 60:40 to 90:10,even more preferably, the compositions have carrageenan/xanthan weightratios of 70:30 to 80:20, with a most preferred weight ratio being75:25. These co-precipitate compositions may optionally be clarified.

The co-precipitated carrageenan/xanthan (also referred to herein as “theco-precipitate”) is suitable for use as a binder, a suspending agentand/or a thickening agent. It is also suitable for use in a dry mix oras a readily dispersing component in dry blends. One advantage of theco-precipitates of the invention is that they are suitable for use overa wide pH range. The pH range over which the co-precipitatedcarrageenan/xanthan product may be used includes acidic, basic andneutral conditions, for example, from about pH 2.0 to about pH 11.

The co-precipitated carrageenan/xanthan can be used in formulations andmay be combined with one or more additional hydrocolloids includingxanthan, carrageenan and carboxymethyl cellulose. The present inventionalso encompasses compositions containing the co-precipitatedcarrageenan/xanthan.

Suitable uses for the co-precipitated carrageenan/xanthan orcompositions containing the co-precipitates are in food, cosmetic,pharmaceutical, industrial and specialty applications. Certain preferredapplications include food and oral care applications where it is usefulas a stable thickener in high ionic environments.

The co-precipitates or compositions containing the co-precipitates areuseful as the base for many food and industrial products such as: agelled or thickened food; a pourable salad dressing; a liquid food orfood additive; a food spread such as a margarine or cheese spread; awater dessert gel; a jam or jelly; a confection; a mayonnaise; a frozendessert; a cosmetic or pharmaceutical liquid; an excipient for use as abinder or disintegrant; a cream or lotion excipient; a dental careproduct; an air freshener gel; a de-icing fluid; and the like. Where thecompositions are used as water dessert gels, they may be in dry form asa mix, or may be in the form of aqueous gels, with or without theadmixed gelling agent. The compositions are typically used in admixturewith one or more flavorants, colorants, sweeteners, food particles,herbs, preservatives, buffering agents, acidifying agents or gelstrengtheners.

Food compositions in which the co-precipitates or compositionscontaining the co-precipitates may be employed include meat (beef,chicken, pork), fish and protein-based products, beverages, dairyproducts, water dessert gels, frozen desserts including ice creams,frozen yoghurts, and novelties, food spreads, pourable or spoonablesalad dressings, soups, sauces, and gravies, acidified foods andacidified beverages, seasonings such as rubs, marinades and spiceblends, gelled foods and thickened foods.

Industrial compositions in which the co-precipitates or compositionscontaining the co-precipitates may be employed include oil fielddrilling and fracture fluids, cements, wall plasters, pesticides,herbicides, pet foods, cleaning and sanitizing compositions and deicingfluids.

Personal Care compositions in which the co-precipitates or compositionscontaining the co-precipitates may be employed include, for example oralcare products, toothpastes, air freshener gels, cosmetic creams andlotions.

Dry blend compositions in which the co-precipitates may be employedinclude compositions comprising the co-precipitate and one or more saltsincluding but not limited to sodium, calcium or potassium salts, saltsof chlorides, lactates, phosphates, citrates and carbonates such assodium carbonate.

Salts, sugar, dextrose, silica, and maltodextrin may be used asstandardizing agents for the co-precipitates and compositions containingthe co-precipitate, as well as in the dry blend compositions. Typically,such compositions are standardized for viscosity and/or gel strength toensure consistency as delivered to the customer since the properties ofsuch products may vary due to the fact that they are obtained fromnatural sources, for example.

The co-precipitates or compositions containing the co-precipitates mayoptionally be admixed with at least one compound selected from the groupconsisting of celluloses, chemically-modified celluloses, seaweedproducts, natural gums, biosynthetic gums, proteins, synthetichydrocolloids, starches, modified starches, dextrins, dextrose, sugars,surfactants, emulsifiers and salts. Similarly, dry blend compositions inwhich the co-precipitates may be employed may contain one or more ofthese additional ingredients. A preferred dry blend composition containsthe co-precipitate in combination with an additional hydrocolloid whichmay be selected from carrageenan, xanthan, carboxymethyl cellulose andmixtures thereof.

When the compositions containing the co-precipitate are foods,industrial, pharmaceutical or personal care products, then thecompositions may contain at least one material selected from the groupconsisting of clays, preservatives, metal oxides, colorants, acidulates,buffers, food particles, herbs, acidifying agents, gel strengtheners,modifiers, emulsifiers, proteins, polypeptides, proteins, amino acids,cultures, and mixtures thereof and optionally a hydrocolloid.

The present invention also includes toothpastes and binder formulationscontaining the co-precipitated carrageenan/xanthan for use intoothpastes. Suitable toothpastes may contain one or more of an abrasiveor polishing agent, a humectant, a binder, a surface active agent,water, and, optionally, other materials that are conventional componentsof toothpaste compositions, such as flavors and sweeteners. The solidand liquid components of a toothpaste composition are formulated toproduce a product that is a consistent, extrudable, creamy material.

The binder builds viscosity, provides a desirable consistency andthixotropy, and prevents separation of the ingredients during storageand use. The binder includes the co-precipitated carrageenan/xanthancomposition of the present invention and optionally additionalhydrocolloids such as cellulose derivatives (“cellulose gums”)including, for example, carboxymethyl cellulose (CMC), methyl cellulose,hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and mixturesthereof; polyvinyl pyrrolidone; xanthan; carrageenans such as iotacarrageenan, kappa carrageenan, kappa-2 carrageenan, lambda carrageenan,and mixtures thereof; guar gum; gum karaya; gum arabic; gum tragacanth;and mixtures thereof.

Carrageenan containing toothpaste is disclosed in Randive, U.S. Pat. No.6,162,418, incorporated herein by reference. Hydrated silica andcolloidal silica may be used as thickeners. Silica thickeners aredisclosed, for example, in Niemi, U.S. Pat. No. 6,342,205, incorporatedherein by reference.

The vehicle of the toothpaste composition is orally acceptable and iscomprised of water and a humectant. The humectant provides mouthfeel andalso prevents the toothpaste composition from drying out. Typicalhumectants are polyols of three to six carbons in which each carbon ishydroxylated, and mixtures thereof, such as glycerol (glycerin),sorbitol, polyethylene glycol, polyoxyethylene glycol, mannitol,xylitol, and other sugar alcohols. Sorbitol and glycerol are preferred.The water is preferably deionized and free of impurities.

Toothpaste compositions also comprise a surface active agent to emulsifyor otherwise uniformly disperse toothpaste components. The surfaceactive agents are typically anionic or nonionic surface active agents,or mixtures thereof. Examples of suitable surface active agents includewater-soluble salts of higher fatty acid monoglyceride monosulfates;higher alkyl sulfates; higher alkyl aryl sulfonates; higher alkylsulfoacetates; higher fatty acid esters of 1,2 dihydroxy propanesulfonate; substantially saturated higher aliphatic acyl amides of loweraliphatic amino carboxylic acid compounds, such as those having 12 to 16carbon atoms in the fatty acid, alkyl or acyl radicals; higher olefinsulfonates, higher alkyl poly-lower alkoxy (of 3 to 100 alkoxy groups)sulfates, and fatty acid soaps. Examples of these anionic surface activeagents include sodium lauryl sulfate (SLS), sodium hydrogenated coconutoil fatty acids monoglyceride monosulfate, sodium dodecyl benzenesulfonate, sodium lauryl sulfoacetates, sodium N-lauryl sarcosinate, andsodium cocate. Suitable types of nonionic surface active agents includechains of lower alkyene oxides such as ethylene oxide and propyleneoxide. A commonly used surface active agent is sodium lauryl sulfate.

The toothpaste composition may comprise a number of other optionalingredients. Agents that provide therapeutic or cosmetic benefits may bepresent, such as enamel hardening agents, tartar control agents,whitening agents, and antibacterial agents. One or more sweeteners andflavorings may be added for consumer satisfaction. Other materials thatare conventional components of toothpaste compositions, such asopacifiers and colorants, may also be present.

Examples of flavorings (flavors, flavoring materials, or flavoringagents) include: menthol; carvone; anethole; methyl salicylate; and theoils of spearmint, peppermint, wintergreen, sassafras, clove, sage,eucalyptus, marjoram, cinnamon, lemon, lime, grapefruit, kumquat,tangerine, and orange. Examples of sweeteners (sweetening agents)include sucrose, lactose, maltose, sorbitol, xylitol, sodium cyclamate,perillartine, L-aspartyl-L-phenylalanine methyl ester (aspartame), andsaccharine.

Pyrophosphate salts having anti-tartar efficacy such as a di-alkali ortetra-alkali metal pyrophosphate salts such as Na₄P₂O₇ (TSPP), K₄P₂O₇,Na₂K₂P₂O₇, Na₂K₂H₂O₇, and K₂H₂P₂O₇, long chain polyphosphates such assodium hexametaphosphate, and cyclic phosphates such as sodiumtrimetaphosphate may be present in the toothpaste composition. Examplesof hardening agents are fluoride salts such as sodium fluoride,potassium fluoride, calcium fluoride, zinc fluoride, stannous fluoride,zinc ammonium fluoride, sodium monofluorophosphate, potassiummonofluorophosphate, and laurylamine hydrofluoride.

Antibacterial agents may also be included in the toothpastecompositions. Especially useful are non-cationic antibacterial agentsthat are based on phenolic and bisphenolic compounds, halogenateddiphenyl ether, benzoate esters and carbanilides, such as sodiumbenzoate; 4-chlorophenol, 2,2′-trichloro-2-hydroxy-diphenyl ether(triclosan); esters of p-hydroxybenzoic acid, especially the methyl,ethyl (ethyl parasept), propyl (propyl parasept), butyl (butylparasept), and benzyl esters; 3,4,4′-trichlorocarbanalide and3,3′,4-trichlorocarbanilide. A preferred antimicrobial agent istriclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol). Nonionicantimicrobial agents such as sesquiterpene alcohols such as merolidoland bisabolol are also useful.

Whitening agents may be present in the toothpaste composition. Usefulwhitening agents are oxidizing agents such as calcium peroxide, ureaperoxide, peracetic acid, and sodium percarbonate. An opacifier, such astitanium dioxide, may be added to make the toothpaste opaque or toincrease its opacity.

The toothpaste composition may also comprise other ingredients that areconventional components of toothpaste compositions, including, forexample, desensitizing agents for sensitive teeth such as sodiumnitrate; orally acceptable colorants such beta-carotene, chlorophyllin,FD&C Yellow #5, FD&C Yellow #6, FD&C Blue #2, FD&C Red #4, FD&C Green#6, FD&C Yellow #10, FD&C Red #40, D&C Green #5, D&C Red #30 lake, andFD&C Blue #1 lake; healing agents, such as rose-seed oil;chelating/sequestering agents, such as citrates; vitamins, such asvitamin C and vitamin E; amino acids; proteins; antibiotics;anti-enzymes; enzymes; pH control agents (buffers); antioxidants; andpreservatives.

The toothpaste composition typically comprises about 0.05 wt % to 3.0 wt% of the binder containing the co-precipitated carrageenan/xanthan,based on the total weight of the toothpaste composition.

Processes for preparing low carrageenan toothpastes are disclosed inBallard, U.S. Pat. No. 6,187,293, incorporated herein by reference.

High moisture toothpastes are also known. The amount of water present ina “high moisture toothpaste compositions” depends to some extent on theabrasive used in the toothpaste compositions. Higher levels of calciumbased abrasives, such as dicalcium phosphate and calcium carbonate, andlower levels of silica are used in toothpaste compositions. Therefore, asilica-based high moisture toothpaste composition will typicallycomprise more water than one that comprises a calcium based abrasive.High moisture toothpastes that comprise iota carrageenan as the binder,and their preparation, are described, for example, in Randive, U.S. Pat.No. 6,159,446, incorporated herein by reference.

Silicon dioxide or silica's may be used in a toothpaste composition forits abrasive properties or for its thickening properties. Examples oftypes of silica's used as abrasives are Zeodent® 113 and Zeodent® 124(J.M. Huber Co., Atlanta, Ga., USA). Examples of silicas used as athickener are Zeodent®, 165, Zeodent®163, and Zeodent® 153 (J.M. HuberCo., Atlanta, Ga., USA). The difference in properties between these twotypes of materials is given in Niemi, U.S. Pat. No. 6,342,205,especially in Tables B and C, and the disclosure that accompanies theseTables. The disclosure of U.S. Pat. No. 6,342,205 is incorporated hereinby reference.

Gadkari in WO2004071321 discloses high moisture, low abrasivitytoothpastes that contain microcrystalline cellulose and less than 8 wt%, typically 7 wt % or less, more typically 1 to 7 wt %, of silicathickener. This toothpaste composition has lower abrasivity thantoothpaste compositions that comprise 8 wt % to 15 wt % silicathickener. In addition, the toothpaste composition comprises less that15 wt %, 1 wt % to less than 15 wt %, in some cases 6 to 10 wt %, ofsilica abrasive. The total amount of silica present is 2 to 22 wt %, insome cases 8 to 18 wt %, and in other cases 10 to 14 wt %.

In high moisture toothpastes, water comprises 45 to 70 wt % of the highmoisture silica containing toothpaste composition. The water content mayalso be 50 to 70 wt % or 60 to 70 wt %, based on the total weight of thetoothpaste composition.

The “as made” viscosity (i.e., the viscosity of the toothpastecomposition after cooling to ambient temperature but before standing formore than several hours, or the “initial viscosity”) of the toothpastecomposition is typically less than 200 mPa-s to avoid sedimentation andto make the composition convenient for use in automated fillingequipment.

When dicalcium phosphate (DCP) is used as the abrasive, the toothpastecomposition typically comprises about 25 to 55 wt %, more typicallyabout 35 to 53 wt % of dicalcium phosphate. When calcium carbonate isused as the abrasive, the toothpaste composition typically comprisesabout 25 to 55 wt %, more typically about 35 to 50 wt %, of calciumcarbonate. Thus, because of the higher level of abrasive in thetoothpaste composition, the amount of water in these high moisturetoothpaste compositions will be less than in one that contains silica.These high moisture toothpaste compositions contain 35 to 60 wt % waterand preferably 40 to 60 wt % water. The binder comprises theco-precipitated carrageenan/xanthan, optionally formulated with acellulose gum, preferably carboxymethyl cellulose, typically at a bindercontent about 0.5 to 3.0 wt % in the toothpaste composition. The amountof binder may be reduced by the presence of a silica thickener, forexample up to about 7 wt %, such as 1.0 to 7.0 wt %, typically about 1.0to 4.0 wt % of a silica thickener, or by the presence of silicathickener and microcrystalline cellulose, for example, 0.5 to 7.0 wt %,typically 0.5 to 2.0 wt % of the silica thickener and 0.5 to 10.0 wt %,typically 1.0 to 3.0 wt % of non-colloidal microcrystalline cellulose,colloidal microcrystalline cellulose, or a mixture thereof. After theabrasive, the water, the binder, and the other ingredients, have beenaccounted for, humectant accounts for the balance of the material.

The toothpaste composition typically comprises about 0.8 to about 3.0 wt%, preferably about 1.0 to about 2.0 wt %, of the surface active agent.When a flavoring is present, the toothpaste composition typicallycomprises about 0.1 to about 2.0 wt %, more typically about 0.5 to about1.5 wt %, of the flavoring. When a sweetener is present, the toothpastecomposition typically comprises about 0.1 to about 2 wt % of thesweetener. When an anti-tartar agent is present, the toothpastecomposition typically comprises about 0.5 to about 8.0 wt % of theanti-tarter agent. When an anti-bacterial agent is present, thetoothpaste composition typically comprises about 0.03 to about 1 wt % ofthe antibacterial agent. When a whitening agent is present, thetoothpaste composition typically comprises about 0.1 to about 5 wt %,preferably about 0.5 to about 2 wt %, of the whitening agent. When apyrophosphate salt is present, the toothpaste composition typicallycomprises about 0.5 to about 8.0 wt %, preferably about 1.5 to about 3wt %, of the pyrophosphate salt. When a hardening agent is present, thehardening agent typically comprises about 0.1 to about 5 wt % of thetoothpaste composition. When present, other ingredients, such as dyesand opacifiers, are present in effective amounts, that is, eachingredient is present in the amount necessary to achieve its particularpurpose.

The toothpaste compositions can be prepared using either the hot processor the ambient process, and either a batch process or a continuousprocess may be used. The ambient process is sometimes called the coldprocess. The hot process is described, for example, in Scott, U.S. Pat.No. 4,353,890, Mulvey, U.S. Pat. No. 4,565,692, and Ballard, U.S. Pat.No. 6,187,293, the disclosures of which are incorporated herein byreference. A continuous process for the manufacture of toothpaste isdisclosed, for example, in Ballard, U.S. Pat. No. 6,187,293, especiallyin FIG. 1 and the accompanying text, the disclosure of which isincorporated herein by reference. A continuous process for themanufacture of toothpaste is also disclosed in Catiis, U.S. Pat. No.5,236,696.

Those skilled in the art will recognize that the co-precipitatedcarrageenan/xanthan of the present invention is suitable for use intoothpaste binders, alone or in admixture with additional hydrocolloids,for the manufacture of a wide variety of oral care products includingopaque, hot process, high moisture, high moisture low abrasive, clear,and striped toothpaste formulations.

The present invention also relates to food treating compositions. Foodproducts treated in accordance with to the present invention can beprepared with the food treating composition of the present invention atone location and shipped to another location, with reduced liquidseepage, leakage or drip loss, for further processing. This is asignificant advantage since the consumer appeal of such products may beadversely affected by the presence of liquid in the meat packaging. Inaddition, liquid seepage into the meat packaging may provide a suitableenvironment for growth of harmful microbes and thus should be avoidedfor this additional reason.

Freshly processed meats may be injected with a brine solution containingco-precipitates in accordance with the present invention. The presentinvention may be used to improve brine retention by 25 to 50% overphosphate and standard carrageenan systems in fresh poultry or pork andto reduce purge in packages. In addition, the co-precipitates of thepresent invention exhibit an excellent tolerance for salts and thus canbe added to the brine solution or other compositions before or after thesalts are added without an adverse performance impact. This simplifiesprocessing and eliminates the potential for errors in formulation ofproducts.

Brine solutions may be made in any suitable conventional manner.Ingredients included in the brine solutions may be added in any suitableform including as a dry blend or dry mix. Sodium chloride and/ortripolyphosphate may be added to the brine to increase the water bindingcapacity of the meat. As demonstrated herein, the present products areeffective in brine solutions with or without phosphates and thus can beemployed in products where eliminating phosphates is a priority.

Moreover, the food treating composition of the present invention permitsthe food to be frozen for subsequent thawing reduced liquid seepage,leakage or drip loss when thawing. Still further, the food treatingcomposition according to the present invention permits the cooking offood with reduced weight loss during cooking to provide an improvedcooking yield. This leads to improved product moisture retention in foodservice applications

By “uncooked food product” is meant a food product, which has notreceived a heat treatment, or has received a heat treatment at one ormore temperatures below the temperature, which renders the proteins infood denatured. This temperature is typically below about 60° C., butvaries according to the protein composition of the food. For meat andpoultry, the heat treatment would comprise one or more temperatures ofpreferably less than about 60° C., and even more preferably less thanabout 55° C. For fish, the heat treatment would comprise one or moretemperatures of preferably less than about 50° C., and even morepreferably less than about 40° C. Thus, uncooked food product includesfood product that is uncooked, such as food product that has not beingsubjected to any treatment temperature, such as chilled or frozen foodproduct, as well as food that has been heated, but not heatedsufficiently to arrive at a protein denaturing temperature, such assemi-warm smoking. Preferably, the food treating composition accordingto the present invention is added at temperatures at which food productsare normally processed, handled, shipped and/or stored.

The co-precipitate composition or compositions containing theco-precipitate can be added to the food product using injectionequipment, mixing, blending, and tumbling equipment. Once thecomposition is in the food product, it can absorb water, thicken or gelto provide an advantageous reduction in seepage, leakage or drip loss ofliquids from the food product.

Other potential advantages which may be achieved using certain brineformulations in accordance with the present invention include improvedconsistency of injected meat products thereby reducing gel pocketformation and increasing permeation into meat for better distribution.These advantages may flow from the ability to provide relatively lowviscosity brines using the co-precipitates of the present invention.This also may lead to a reduced potential for blow outs and muscle tearsin the meat products since the lower viscosity brine is less likely toexert localized high forces on the meat products during injection. It isalso expected that the low viscosity brines of the present inventionwill improves pumpability, reduce equipment wear and increasethroughput.

If injection equipment is utilized to add the composition to the foodproduct, the viscosity of the composition is preferably suitable forinjection using conventional injection equipment, such as a FomacoMultineedle Injector Equipment model FGM 20/40. For example, it ispreferred that the composition have a viscosity of about 1 to 1000 cps,about 5 to 800 cps, about 10 to 800 cps and, most preferably, about 20to 800 cps. In instances where the composition is to be mixed with thefood, such as in high shear equipment, the viscosity of the compositioncan be higher. Thus, if the incorporation of the composition will takeplace in a grinder, cutter or emulsifiers, e.g. colloid mills, thenhigher concentrations of the co-precipitate can be utilized to providehigher viscosity compositions. As discussed above, the concentration ofpolysaccharide included in the food treating composition can be varieddepending upon the manner of addition to the food product, and can alsobe varied depending upon the specific co-precipitate or compositioncontaining the co-precipitate utilized in the composition. If thecomposition is to be added using injection equipment, then it ispreferred that the co-precipitate be included in the brine compositionat a concentration that permits the use of injection equipment, such asup to about 5 wt %, more preferably about 0.01 to 2 wt %, morepreferably about 0.1 to 1 wt %.

The co-precipitate or composition containing the co-precipitate ispreferably not gelled during preparation, but could potentially begelled in situ after incorporation into the food product. Thus,typically the brine composition includes the co-precipitate, but doesnot include components therein that cause gelling of the composition atthe time of preparation and/or is not prepared at conditions that enablethe composition to gel. For example, the brine composition can containcomponents that would, under certain conditions, influence gelling ofthe co-precipitate composition; however, these components are presentunder conditions that do not enable them to gel the solution. Thus, thecomponents may be undissolved, such as insoluble at the particulartemperature or pH, such as some poorly soluble calcium salts, includingcalcium sulphate. The components may be in an inactive form during thepreparation of the composition, such as present in the composition as anencapsulated active ingredient which will become active only at aparticular temperature or pH.

The food treating compositions of the present invention may optionallybe gelled in a food product, if desired. After addition to the foodproduct, depending upon the particular composition of theco-precipitate, conditions could be present in the food product and/orconditions may be modified in the food product to cause gelling of thecomposition within the food product, if desirable, though gelation maynot be necessary to achieve the desired improvements in the foodproduct. For example, gelation could occur during cooking, in which casethe gel may add some viscosity, and thereby partially reduce cookingloss. Thus, liquid seepage or drip loss from the food product may bereduced during cooking as well as during distributing and handling toprovide higher cooking yields.

The food products can be any type of meat, poultry or seafood, from wildor domesticated animals with or without bones or skin, whole or inparts, minced, comminuted or emulsified, in any state of natural, fresh,chilled frozen and jerked meats, or in another condition, which isun-cooked.

The invention will now be described with respect to certain exampleswhich are merely representative of the invention and should not beconstrued as limiting thereof.

Test Methods

Viscosity: A 1.5% by weight aqueous solution of the carrageenan/xanthansample are prepared by mixing and heating to 85° C., holding for 15minutes, and then cooling to 75° C. before measuring the viscosity usinga Brookfield LV viscometer. The viscosity was measured using an aqueoussolution containing 1.5% by weight of carrageenan or 1.0% by weight ofxanthan following the same method unless otherwise stated.

Moisture content is determined by weight loss upon drying for 1 hour at110° F. in a oven.

Gel strength—Gels are prepared by heating the solution in a boilingwater bath with continuous mechanical agitation to a temperature of 82°C. The weight is adjusted for evaporative losses using distilled waterand the solution is well mixed. The hot solution is poured into threedishes (70 mm×50 mm) and placed in a 25° C. water bath for one hour. Thegels are inverted and placed in the test instrument so that the plungerwill contact the center of the gel. The break force strength (in gramsforce) and the penetration distance (in centimeters) of the probe aredetermined using an Instron Materials testing instrument Model 4442, 10kg capacity, with a 10.9 mm diameter tapered metal plunger at a descentspeed of 70 mm/minute Water gel compositions for testing include a 2%water gel which uses 2% by weight of gum solids in distilled water; a“1%+1” water gel which uses 1% by weight of gum solids plus 1% by weightof potassium chloride in distilled water and a “1%+1+1” water gel whichuses 1% by weight of gum solids plus 1% potassium chloride and 1% byweight of calcium chloride in distilled water. Milk gels are prepared bymixing the sample in cold, homogenized, whole milk and heating to 82° C.After adjusting for evaporative losses, the hot solution is poured intodishes and placed in a 10° C. water bath for one hour prior to gelstrength testing with the Instron Model 4442 as for water gels exceptthat a 21.5 millimeter diameter tapered metal plunger is used.

Acid stability: A 1.5% solution was made with mixing and heating to 82°C. followed by cooling to 75° C. The sample was placed in a bath at 75°C. and 5.04 grams of sodium phosphate and 6.2 grams of sodium citratewere stirred in. The viscosity was measured (time 0) using a BrookfieldLV viscometer at 30 rpm. The viscosity and pH (=3.8) were re-testedafter 7.5, 15, 30, 45, 60, 75 and 90 minutes at 75° C. The rate ofhydrolysis is calculated as the decrease in viscosity per minute.

Particle size was measured using a Horiba LA-910 laser scatteringparticle size analyzer.

Brabender testing: The hydration and viscosity behavior ofco-precipitated carrageenan/xanthan in aqueous solution or in productformulations are measured using a Brabender viscometer (modelViskograph-E). The sample is stirred while heated, held at a maximumtemperature, and then cooled. The heating and cooling rates are set at1.5° C./minute. The cup rotational speed on the Brabender viscometer isset at 75 rpm. Brabender hydration profiles are determined using a 2 wt% sample in de-ionized water. The test solution uses the followingheating/cooling profile: hold for 20 minutes at 25° C., heat to 95° C.,hold at 95° C. for 10 minutes, cool to 25° C., and hold at 25° C. for 5minutes. The hydration is also characterized in a model toothpasteelixir containing de-ionized water (42.8 wt %), sorbitol (33.1 wt %),glycerin (19.5 wt %), sodium monofluoro phosphate (2.1 wt %), binder(1.6 wt %), tetra sodium pyrophosphate (0.5 wt %), and sodium saccharine(0.4 wt %) The test solution uses the following heating/cooling profile:hold for 5 minutes at 25° C., heat to 82° C., hold at 82° C. for 1minute, cool to 25° C., and hold at 25° C. for 5 minutes.

Toothpaste Sample Preparation: Toothpaste compositions are preparedusing the hot process by the following procedure:

(1) The binder is dispersed into the humectant with a high-speed stirrerand stirred for about 10 minutes.

(2) The water is heated to about 80° C. and added to thehumectant/binder mixture with stirring continuing for 15 minutes whilethe temperature is maintained at 60-70° C.

(3) The dry ingredients, such as sodium saccharin, sodium benzoate, etc,exclusive of the abrasive are dry blended. The dry blend is stirred intothe binder slurry and stirring is continued for 15 minutes while thetemperature is maintained at 60-70° C.

(4) The resulting elixir is transferred to a low speed Ross mixer with avacuum attachment. The Ross mixer is a double planetary gear, two-paddlemixer, which operates at 20 to 100 revolutions per minute and can beoperated under vacuum.

(5) The abrasive is added to the elixir forming a paste and the paste ismixed for 15 minutes under vacuum (at least 720 mm Hg.).

(6) Flavoring is then added and the paste is mixed for 10 minutes in theRoss mixer under full vacuum.

(7) Surfactant, such as sodium lauryl sulfate (SLS), is then added andmixing of the paste is continued under vacuum for 20 minutes.

(8) A sample is withdrawn for testing, and the batch is discharged forfilling tubes or other dispensers.

Toothpaste viscosity is measured with a T-Bar spindle E at 5 rpm using aBrookfield DVII Viscometer equipped with a Helipath attachment. Thesample was first equilibrated at ambient temperature (25° C.). Viscositywas measured by placing the spindle directly into a tube containing30-40 g of the toothpaste composition. The stationary spindle waspositioned within the sample. The viscometer was turned on and readingswere recorded every 10 seconds for a total period of 1 minute, for atotal of six readings, which were then averaged.

Cuban Test—In the Cuban test (also termed the “Rack” test), thetoothpaste is squeezed from a tube through a fixed orifice across a gridof parallel rods, adjacent pairs of rods of which are spaced apart atincreasing distances from one another. The test results are expressed asthe greatest space number (numbers are from 1-12) which represents thelongest distance between rods that support the dentifrice ribbon withouthaving it break. The rack is about 300 millimeters (mm) long and about100 mm wide. The stainless steel rods are spaced at increasing distancesapart starting at a spacing of 3 mm between rods 1 and 2 (space number1). The distance between pairs of rods increases by 3 mm from pair topair. Thus the distance between rods 2 and 3 is 6 mm, and the distancebetween the twelfth and thirteenth rods (space number 12) is 39 mm. Fortoothpastes that are not high moisture toothpastes, rack ratings orspace numbers of 1-2 and 9-12 are not acceptable, rack ratings or spacenumbers of 3 and 8 are acceptable and rack ratings or space numbers of4-7 are good. The Cuban test procedure is carried out as follows: (1) Anozzle with 3.2 mm diameter opening is fixed to a toothpaste tube filledwith a toothpaste composition to be tested. (2) The tube filled withtest toothpaste composition and having the nozzle attached is held at anangle of 45° to the rack device. Pressure is applied at the bottom ofthe tube and a uniform ribbon of paste is squeezed from the tube. Whilethe ribbon of paste is extruded from the tube the tube is moved acrossthe rack in a straight line. The time to stretch the ribbon of pasteover the rack is usually about two to four seconds. If the ribbon breaksbefore the entire rack is traversed, the procedure is repeated. (3) Theribbon is allowed to stand for 30 seconds. At that time, the point orspace number at which the ribbon breaks is recorded as the rack ratingor Cuban value. (4) The test is performed three times and the averagereading is recorded, rounding off to the nearest complete figure.

EXAMPLES Example 1 Preparation of Co-Precipitated Carrageenan/Xanthan

Co-precipitated iota carrageenan/xanthan samples were prepared bypre-dissolving xanthan having a 1 wt % viscosity of 2800 cP and a pH of7.3 in deionized water and subsequently adding the xanthan solution toan alkaline iota carrageenan solution. For samples 1-1 to 1-4, thexanthan was dissolved by dispersing in water to form a 0.5 wt % solutionand heating to 82° C. with constant agitation. This xanthan solution wasthen combined with a 1.5 wt % iota carrageenan solution. (Thehydrocolloid concentrations are based on the weight of a moisture-free,gum content basis for the hydrocolloid.) The two solutions were combinedat equal volumes to provide a ratio of 75 parts of iota carrageenan to25 parts of xanthan. The mixture was recovered by precipitation in 75%isopropyl alcohol/25% water, dried under heat and vacuum, then ground toa particle size of less than 100 mesh. Sample 1-5 was prepared in asimilar manner except that the xanthan solution was prepared at a higherconcentration of 0.8 wt % and 1 part of this xanthan solution wascombined with 1.66 parts of a 1.5 wt % iota carrageenan to provide aratio of 75 parts of iota carrageenan to 25 parts of xanthan. The dryco-precipitate was dissolved in deionized water and viscosity and pH wastested. The results are reported in Table 1.

TABLE 1 Co-precipitated carrageenan/xanthan (75:25 weight ratio, gumsolids) Viscosity of co- pH of co- Iota precipitated precipitatedXanthan Carrageenan product (cP) product 1-1 Filtered Filtered 200 10.71-2 Unfiltered Unfiltered 280 11.1 1-3 Unfiltered Filtered 205 11.0 1-4Unfiltered Filtered 433 10.7 1-5 Unfiltered Filtered 345 11.1

Example 2 Brabender Testing

Brabender hydration profiles were determined by measuring the viscosityresponse at a cup speed of 75 rpm during a temperature profile includingboth heating and cooling for a 2 weight % aqueous solution preparedusing 490 grams of deionized water and 10 grams of the co-precipitatedproduct from Example 1-3 or, as a comparative example, a 2 weight %aqueous solution prepared using 10 grams of a proportional “blend” of75% carrageenan and 25% xanthan in 490 grams of deionized water (FIG.1). The initial hydration profiles were very similar for both samples indeionized water at temperatures below about 40° C. During the heatingstage, the co-precipitated product of the present invention exhibited ahigher viscosity between 50° C. and 70° C. compared to the comparative“blend” sample. Similarly upon cooling, the co-precipitated material ofthe present invention was observed to provide a higher viscosity thanthe “blend” sample.

The hydration behavior of the co-precipitated sample of Example 1-3 and,as a comparative example, the proportional “blend” sample of 75 wt %carrageenan and 25 wt % xanthan were similarly characterized in a modeltoothpaste elixir containing 42.8 wt % de-ionized water, 33.1 wt %sorbitol, 19.5 wt % glycerin, 2.1 wt % sodium monofluorophosphate, 1.6wt % of the sample, 0.5 wt % tetra sodium pyrophosphate, and 0.4 wt % ofsodium saccharine (FIG. 2) prepared by the method described above.

Example 3 Drip Loss Comparison in Injected Fresh Pork Loin

Brine samples were prepared using 86.7 wt % water, 8.3 wt % salt (NaCl),2.5 wt % sodium tripoly phosphate and 2.5 wt % sample, where the samplewas one of iota carrageenan (non-inventive control), the co-precipitated75:25 iota carrageenan/xanthan (sample 1-3 of the present invention)and, as a comparative example, a brine prepared using a proportional“blend” of 75 wt % iota carrageenan and 25 wt % xanthan. The brinesolution viscosity was similar for the iota carrageenan (control) andthe co-precipitated iota carrageenan/xanthan (sample 1-3) and thetargeted injection was achieved for both.

TABLE 2 Viscosity of phosphate brines with a 75:25 co-precipitate(“cpt.”) or with a dry blend (“blend”) 5 rpm 10 rpm 50 rpm 100 rpm 1.25%cpt.    800 cP   400 cP  160 cP  80 cP 1.25% blend 177,000 cP 88,400 cP17760 cP 8840 cP 1.65% cpt.   1600 cP   800 cP  240 cP  120 cP 1.65%blend 178,000 cP 89,200 cP 18,080 cP  9080 cP 3.25% cpt.  20,200 cP10,200 cP  2240 cP 1180 cP 3.25% blend 222,000 cP 116,000 cP  27040 cP14600 cP 

Brine viscosity was measured using Brookfield DVT III RT (spindle #7, 5°C.).

The brine solution prepared with the “blend” (comparative example) wasmore viscous, however, and somewhat difficult to pump. Sections of porkloins were injected with brine using a Fomaco FGM 20/80 injectorequipped with eighty 3-mm pencil point needles to a target weight of125% (the percentage of the weight after injection relative to theweight of the pork loins prior to injection), then weighed and placed onracks and re-weighed at intervals to obtain a weight loss as a functionof time reported as drip loss (the drip loss is the percentage weightloss determined by measuring the remaining weight at a time afterinjection and comparing it to the weight of the pork loin immediatelyafter injection).

The average injection achieved using the brine prepared from the “blend”(comparative example) averaged 119%, which was somewhat lower than the125% targeted injection level. As shown in FIG. 3, the drip loss of porkinjected with a brine containing 2.5 wt % co-precipitated iotacarrageenan/xanthan (example 1-3) showed reduced drip loss with timecompared to the drip loss of pork injected with either a brinecontaining 2.5 wt % commercial iota carrageenan (non-inventive controlexample) or pork injected with a brine containing 2.5 wt % of the“blend” (comparative example). After 24 hours refrigerated hold for driploss, the pork loins were cooked with a ramped heating to an internaltemperature of 165° F. (74° C.). The overall cooked process yield, i.e.,the final cooked weight less the initial weight (before injection)divided by the initial weight (before injection), is reported in FIG. 4.The highest cooked process yield was obtained for the pork loins whichhad been injected with brine using the brine containing theco-precipitated carrageenan/xanthan.

Example 4 Drip Loss Comparison in Injected Whole Chickens

The brine compositions used in Example 3 were injected into fresh wholechickens using a Fomaco FGM 20/80 injector equipped with eighty 3-mmpencil point needles to a target weight of 120%, then weighed and placedon racks and re-weighed at intervals to obtain a drip loss after fifteenminutes, thirty minutes, one hour, and two hours. The chickens were thencovered and refrigerated and stored in a row of five stacked three high(per group of fifteen tested for each brine) to simulate shipment. Theweight loss was measured after one, three, five, and seven days. Thetest was repeated in a second separate injection trial using a secondbatch of the same brines. In both cases, the brine prepared using the“blend” (comparative example) had a higher viscosity and could only beinjected to a target weight of 115% as compared to a target weight of120% which was achieved by injection of the brines using the iotacarrageenan (non-inventive control example) and the co-precipitatedblend of example 1-3, respectively. Table shows that the viscosity ofphosphate brines prepared using the 75:25 co-precipitate vs. a dry blendcomposition are significantly lower in viscosity. The co-precipitateprovides a desirable low viscosity with acceptable suspension at a rangeof concentrations. Processing advantages of using a lower viscositybrine include less plugging of injector needles, improved processabilityto reproducibly inject the same level, and more uniform distribution ofbrine within the meat (to avoid the formation of gel pockets).

As shown in FIG. 5, which shows the average of the two trials, the driploss of chicken injected with a brine containing 2.5 wt %co-precipitated iota carrageenan/xanthan (example 1-3) showed the lowestdrip loss with time when compared to the drip loss of chicken injectedwith the brine containing 2.5 wt % commercial iota carrageenan(non-inventive control example) and the drip loss of chicken injectedwith a brine prepared using 2.5 wt % of the “blend” (comparativeexample). After seven days, the drip loss for injected brines containingthe co-precipitated sample (example 1-3) showed a significant advantagesince the drip loss was 2.25% lower than the drip loss for the chickensinjected with the brine containing only iota carrageenan (non-inventivecontrol example) and 11% lower than for the chickens injected with thebrine containing the “blend” (comparative example).

Example 5 Co-Precipitates of Xanthan with Different Types ofCarrageenans

Aqueous solutions were prepared with the following hydrocolloids: kappacarrageenan with a 1.5 wt % viscosity of 22 cP and pH=9.1; iotacarrageenan with a 1.5 wt % viscosity of 30 cP and a pH=9.1; lambdacarrageenan with a viscosity of 105 cP and a pH of 8.7; iota carrageenanwith a 1.5 wt % viscosity of 38 cP and a pH of 10); and a xanthan with a1 wt % viscosity of 2800 cP and a pH of 7.3. Mixtures at specific weightratios were prepared by dispersing the carrageenan and xanthan in waterat appropriate ratios to provide 1.75% to 2.0% solids content at roomtemperature. Samples were heated to 90° C. with mixing. If required, thepH was adjusted to within the range of 8 to 10 with a 10% solution ofsodium hydroxide. After 1 hour of mixing, the co-precipitate wasrecovered by co-precipitation in an isopropyl alcohol/water solution,dried and ground to a particle size of less than 100 mesh. The dryco-precipitate was tested for viscosity, pH, and gel strength (asreported in Table 3) and for acid resistance compared to a dry blendmixture of the same composition (as reported in Table 4). The acidresistance as determined by viscosity loss at pH 3.8 is superior for theco-precipitate compared to the dry blend. In addition, the results ofTable 3 illustrate the formulating flexibility provided by the presentcompositions as can be seen, for example, by the fact that a 90:10composition can be a liquid in a milk gel. “NT” indicates “not tested.”

TABLE 3 Gel Properties of Co-precipitated Xanthan Gum with VariousCarrageenans 3A 3B 3C 3D 3E 3F 3G Co-precipitate Components Carrageenan(Cgn) Kappa Iota Lambda Iota Iota Iota Iota type (22 cP) (30 cP) (105cP) (41 cP) (38 cP) (38 cP) (38 cP) Carrageenan to 75:25 75:25 75:2575:25 90:10 75:25 60:40 xanthan ratio Solids before 2.0 2.0 2.0 1.75 2.01.75 2.0 precipitation (%) Viscosity before 960 1080 1640 295 600 550130 precipitation (cP) Co-precipitate Solution Properties PercentMoisture 3.63% 6.93% 5.95% 11.74% NT NT NT 1.5 wt % 380 430 542 265 700270 105 viscosity (cP) pH 7.1 9.9 8.6 9.7 9.3 9.3 8.8 2% water gel 96gf, 97 gf, Fluid 32 gf, 44 gf 42 gf 54 gf, 0.9 cm 2.2 cm 2.1 cm 2.0 cm2.1 cm 2.1 cm 1% + 1 water gel 249 gf, 108 gf, Fluid 82 gf, 71 gf, 89gf, 122 gf, .22 cm 1.8 cm 1.9 cm 1.9 cm 1.9 cm 1.9 cm 1% + 1 + 1 watergel 323 gf, 120 gf, 52 gf, 116 gf, NT NT NT .22 cm 2.1 cm 2.1 cm 2.0 cmmilk gel 50 gf, 62 gf, Fluid 22 gf, Fluid 34 gf, 71 gf, 0.4 cm 1.1 cm.67 cm 0.6 cm 1.1 cm gf = grams force exerted by the metal plunger

TABLE 4 Acid Resistance of Co-precipitates vs. Corresponding Dry BlendCompositions Co-precipitate 3A 3B 3C 3D Carrageenan Kappa Iota LambdaIota type (22 cP) (30 cP) (105 cP) (41 cP) Carrageenan to 75:25 75:2575:25 75:25 Xanthan Ratio (wt) Acid resistance −1.3 −2.0 −2.9 −1.7 ofDry Blend* Acid resistance 0 −1.2 −1.8 −1.0 of Co- precipitate**hydrolysis rate indicated as cP/minute (×1000)

Example 6

Xanthan was dispersed at about 1 wt % in water using a high shear mixer.The xanthan solution and an alkaline carrageenan solution were meteredinto a continuous stirred tank at rates sufficient to produce 1.0 to1.5% solids mixtures of 75% carrageenan and 25% xanthan or 90%carrageenan and 10% xanthan. The solution was subsequently evaporated toslightly concentrate the solids, then coagulated in a mixture ofisopropyl alcohol and water, centrifuged, pressed and vacuum dried toremove the alcohol, batch dried to a moisture content of below 5% andground to a particle size less than 100 mesh.

TABLE 5 Properties of Carrageenan/Xanthan Co-precipitates Sample 21 2223 Carrageenan (%) 90 74 75 1.5 wt % viscosity (cP) 36 60 44 1.5 wt % pH8.8 8.6 8.7 % through 100 Mesh 99.8 99.7 99.8 Milk Gel 69 64 53 Meanparticle size 79 87 33 (micrometers) Median particle size 75 78 18(micrometers)

Example 7 Drip Loss Comparison in Injected Whole Chicken

The following brines were prepared, with all percentages by weight:

Brine A: 88.75% water, 7.5% sodium chloride, 2.5% sodiumtripolyphosphate and 1.25% of co-precipitate with a 75:25 ratio byweight carrageenan to xanthan

Brine B: 88.75% water, 7.5% sodium chloride, 2.5% sodiumtripolyphosphate 0.375% of sodium carbonate and 0.875% of co-precipitatewith a 75:25 ratio by weight carrageenan to xanthan

Brine C, 88.75% water, 7.5% sodium chloride, 1.875% dextrose, 0.625%sodium citrate, 0.375% of sodium carbonate and 0.875% of co-precipitatewith a 75:25 ratio by weight carrageenan to xanthan

Brine D: 88.75% water, 7.5% sodium chloride, 2.5% dextrose, 0.375% ofsodium carbonate and 0.875% of co-precipitate with a 75:25 ratio byweight carrageenan to xanthan.

Fresh three pound whole chickens were injected with brine using a FomacoFGM 20/80 injector equipped with eighty 3-mm pencil point needles toabout ˜120% (vs. a target of 125% where 100% corresponds to the weightof meat prior to injection), weighed to determine amount of brineinjected, placed on racks and re-weighed at intervals to obtain a driploss after fifteen minutes, thirty minutes, one hour, and two hours. Thechickens were then covered and refrigerated, stored in a row of fivestacked three high (per group of fifteen tested for each brine) tosimulate shipment.

TABLE 6 Drip Loss versus Time Sample 22 Pilot sample 22′ Brine injected(%) 21.1 21.6 21.8 15 minutes (% loss) 1.96 1.78 1.41 30 minutes (%loss) 3.13 3.05 2.17 1 hour (% loss) 4.14 3.84 3.44 2 hour (% loss) 4.644.44 4.43 1 day (% loss) 6.01 5.60 5.16 3 days (% loss) 7.15 6.71 6.79 5days (% loss) 8.63 7.90 7.58 7 days (% loss) 9.39 9.31 8.66 Cook yieldafter 7 days 87.8% 90.9% 90.7%

TABLE 7 Drip Loss versus Time Sample 23 Pilot sample 23′ Brine injected(%) 20.8 20.2 20.7 15 minutes (% loss) 1.71 1.46 1.16 30 minutes (%loss) 2.90 2.43 1.96 1 hour (% loss) 3.91 3.15 2.42 2 hour (% loss) 4.663.91 3.10 1 day (% loss) 5.43 4.53 4.24 3 days (% loss) 6.14 6.51 5.76 5days (% loss) 7.39 7.30 6.68 7 days (% loss) 9.76 9.22 9.10 Cook yieldafter 7 days 88.6% 88.8% 90.4%

TABLE 8 Drip Loss versus Time Sample 23 23 No phosphate 23 No phosphateor citrate phosphate Brine injected (%) 23.6 20.5 20.1 15 minutes (%loss) 2.64 1.64 1.64 30 minutes (% loss) 3.08 2.15 2.51 1 hour (% loss)3.56 2.79 2.93 2 hour (% loss) 4.45 3.14 3.28 1 day (% loss) 5.39 4.104.30 3 days (% loss) 6.65 5.16 5.30 5 days (% loss) 7.29 6.03 5.88 7days (% loss) 7.77 6.64 6.63 Cook yield after 7 days 90.7% 90.9% 87.8% %loss is the percentage of the weight lost relative to the initialinjected weight

The terms and expressions which have been employed are used as terms ofdescription and not of limitation. There is no intention in the use ofsuch terms and expressions of excluding any equivalents of the featuresshown and described or portions thereof. It is recognized, therefore,that various modifications are possible within the scope and spirit ofthe invention. Accordingly, the invention incorporates variations thatfall within the scope of the following claims.

1. A co-precipitate hydrocolloid composition consisting essentially of at least one carrageenan and at least one xanthan, wherein said carrageenan to xanthan ratio is from 60:40 to 95:5, based on weight percentage.
 2. A co-precipitate hydrocolloid composition as claimed in claim 1, consisting of at least one carrageenan and at least one xanthan, wherein said carrageenan to xanthan ratio is from 60:40 to 95:5, based on weight percentage.
 3. The co-precipitate hydrocolloid composition of claim 2, wherein said carrageenan to xanthan ratio is from 60:40 to 90:10, based on weight percentage.
 4. The co-precipitate hydrocolloid composition of claim 2, wherein said carrageenan to xanthan ratio is from 70:30 to 80:20, based on weight percentage.
 5. The co-precipitate hydrocolloid composition of claim 2, wherein said carrageenan to xanthan ratio is about 75:25, based on weight percentage.
 6. The co-precipitate hydrocolloid composition of claim 1, wherein said carrageenan comprises a carrageenan selected from the group consisting of kappa carrageenan, kappa-2 carrageenan, iota carrageenan, lambda carrageenan, mu carrageenan, nu carrageenan and mixtures thereof.
 7. The co-precipitate hydrocolloid composition of claim 1, wherein said carrageenan is iota carrageenan.
 8. A composition comprising the co-precipitate hydrocolloid composition of any one of claims 1-2.
 9. The composition of claim 8, wherein the composition further comprises at least one compound selected from the group consisting of celluloses, chemically-modified celluloses, seaweed products, natural gums, biosynthetic gums, proteins, synthetic hydrocolloids, starches, modified starches, dextrins, dextrose, sugars, surfactants, emulsifiers, and salts.
 10. The composition of claim 8, wherein said composition is toothpaste and said toothpaste further comprises at least one of water, a humectant, a surfactant and an abrasive.
 11. The toothpaste composition of claim 8, wherein said carrageenan is iota carrageenan.
 12. The composition of claim 8, wherein said composition is dry and further comprises a salt.
 13. The composition of claim 8, wherein said composition is dry and further comprises an additional hydrocolloid.
 14. The composition of claim 13, wherein said additional hydrocolloid is at least one member selected from the group consisting of carrageenan, xanthan, and carboxymethylcellulose and mixtures thereof.
 15. The composition of claim 8 wherein said composition is a food and further comprises at least one material selected from the group consisting of colorants, acidulates, buffers, food particles, herbs, acidifying agents, gel strengtheners, modifiers, emulsifiers, proteins, polypeptides, proteins, amino acids, cultures, and mixtures thereof and optionally a hydrocolloid.
 16. The composition of claim 8 further comprising at least one of at least one additional hydrocolloid, a standardizing agent, an abrasive, a filler, a surfactant and mixtures thereof.
 17. The composition of claim 8, wherein said carrageenan is iota carrageenan.
 18. The composition of claim 8, wherein the composition is selected from the group consisting of meats, fish and protein-based products, beverages, dairy products, water dessert gels, frozen desserts, food spreads, pourable or spoonable salad dressings, soups, sauces, and gravies, acidified foods, acidified beverages, rubs, marinades and spice blends, gelled foods and thickened foods.
 19. The composition of claim 8, wherein the composition is selected from the group consisting of oil field drilling and fracture fluids, cements, wall plasters, pesticides, herbicides, pet foods, cleaning and sanitizing compositions and deicing fluids.
 20. The composition of claim 19, wherein the composition further comprises one or more components selected from the group consisting of clays, preservatives, metal oxides, colorants, acidulates, buffers, food particles, herbs, acidifying agents, gel strengtheners, modifiers, emulsifiers, proteins, polypeptides, proteins, amino acids, cultures, and mixtures thereof and optionally a hydrocolloid.
 21. The composition of claim 8, wherein the composition is selected from the group consisting of oral care products, toothpastes, air freshener gels, cosmetic creams and lotions.
 22. The composition of claim 21, wherein the composition further comprises one or more components selected from the group consisting of clays, preservatives, metal oxides, colorants, acidulates, buffers, food particles, herbs, acidifying agents, gel strengtheners, modifiers, emulsifiers, proteins, polypeptides, proteins, amino acids, cultures, and mixtures thereof and optionally a hydrocolloid.
 23. A process for preparing a co-processed hydrocolloid comprising the steps of mixing hydrated hydrocolloids comprising at least one carrageenan and at least one xanthan, and co-precipitating the mixed hydrocolloids to recover a co-precipitated hydrocolloid from the aqueous medium.
 24. The process of claim 23, wherein the co-processed hydrocolloids are co-precipitated with alcohol and recovered from an alcohol-containing bath.
 25. The process of claim 23, wherein the carrageenan is iota carrageenan.
 26. A process for treating an uncooked food product comprising at least one of meat, seafood and poultry, comprising the step of adding to the uncooked food product an aqueous composition comprising the co-precipitated composition of claim
 1. 27. A process for treating an uncooked food product comprising at least one of meat, seafood and poultry, comprising the step of adding to the uncooked food product an aqueous composition comprising the co-precipitated composition of claim
 2. 28. A process as claimed in claim 26, wherein the food product comprises meat.
 29. A process as claimed in claim 26, wherein the food product comprises seafood.
 30. A process as claimed in claim 26, wherein the food product comprises poultry.
 31. A process as claimed in claim 26, wherein the aqueous composition is added by injection.
 32. A process as claimed in claim 26, wherein said carrageenan is iota carrageenan. 